Manufacture of sulfate of copper and caustic alkalis.



No. 829,778. PATENT ED AUG. 28, 1906; H. M. GRANIER.

MANUFACTURE OF SULFATE OF COPPER AND GAUSTIG ALKALIS.

APPLICATION FILED MAB.12,1'904.

8 2 SHEETSSEBET 2.

J \/a l f 8 f r 7%5266666 ,Zizaazfa? facture of Sulfate of UNITED STATES PATENT OFFICE.

HENRI MICHEL GRANIER, or VILLEMOMBLE, SEI'NE, FRANCE.

Specification of Letters Patent.

Patented Aug. 28, 1906.

Applioati0i1 filed March 12, 1904. erial No. 197.879.

To all whom it may concern:

Be it known that I, HENRI MICHEL GRA- NIER, a citizen of the French Republic, and a resident of No. 3 Avenue des Ecoles, Villemomble, Seine, France, have invented a oer.- tain new and useful Process for the Manukalis by the Electrolysis of Alkaline Chlorids, of which the following is a specification.

It is wellknown that if an aqueous solution of an alkaline chlorid-for instance, chlorid of sodiumbe electrolyzed by means of electrodes .which are unaffected by the electrolyte soda is produced at the negative pole and chlorin is evolved at the positive pole; but the presence of chlorin and soda, notwithstanding the best diaphragms, give rise to the formation of hypochlorites and chlorates, and in consequence of secondary electrolytic reactions oxygen is evolved at the positive .pole and combines with the chlorin to form oxygen compounds of chlorin, which destroy very quickly the anodes and the diaphragms.

Now this invention has for its object to provide an improved process which remedies comlpletely those two drawbacks.

v T e improved process allows of producing sulfate of copper as well as caustic alkalis.

It consists, substantially, in em loying anodes of copper or copper alloys and in employing as the electrolytes an alkalin chlorid at the negative pole and a mixture of alkaline chlorid saturated with cuprous chlorid at the positive pole.

The cathodes may be composed of any material which is not affected by the alkali that is formedsuch as, for instance, iron.

' Under these conditions the chlorin which is evolved at the positive pole forms cuprous chlorid, (Cu Cl which is precipitated in the '1 form of a white powder that is deposited in the path of the positive li uid during the circulation of the latter. T e caustic alkali is deposited at the negative electrode, as in the other processes; but in the present process the chlorin is eliminated as soon as its is produced, thereby obviatin the-formation of oxygen compounds of ch orin. The anodes and the diaphragms are thus no longer destroyed. On the contrary, the consumption of the anodes enters as profit into the manufacture, because it gives rise to an industrial product. In fact, the copper of the anodes combining to form cuprous chlorid (Cu Cl can be converted very easily into sulfate of Copper and Caustic Alcopper. The chlorid-of-copper powder is collected and washed in water. In order to obtain. sulfate of copper therefrom, it is merely necessary to treat this dry powder with concentrated sulfuric acid up to calcination-point. Hydrochloric acid isevolved and is collected. by the ordinary means of condensation, and a white powder of anhydrous sulfate of copper is produced which only requires to be dissolved in water and recovered by crystallization.

In cases where the anodes are composed of alloys (such as copper and zinc) and used with a saturated aqueous solution of on ric chlorid and sodium chlorid the cuprous o lorid will be precipitated and the zinc will remain in solution.

The process may conveniently be carried into effect by means of the improved electrolyzing apparatus illustrated in the accompanying drawings, in which Figure 1 is a vertical section thereof. Fig.

' partly in section, on the line A B 2 is a plan, of Fig. 1. Figs. 3 and 4 are two verticalcross-sections taken, respectively, on the line C D and E F of Fig. 1.

In the figures the same letters of reference indicate the same parts.

As shown in the drawings, the improved electrolyzing apparatus comprises a vessel a, composed of cast-iron coated with ebonite or of any other insulating substance, whose longitudinal walls areformed internally with guides I), designed to keep the frames 0 in place. Each of these latter is rovided on each of its two faces .with a diap a m (1, so that each'frame, with its two diapIiragms, forms a compartment for the reception of an anode. The frames 0 are mounted upon any suitable support. By way of example, the

beams c are shown for such pur ose.

The cathodes are arranged in t e spaces 6, comprised between the anode or positive compartments. anodes are operative on both faces.

The anodes and the cathodes are not shown in the drawings in order to avoid complicatin the latter. The positive liquid is supplie in a clear state to the electroly'zer throu h a supply-pipe f, from which are branc ed small pipes g, discharging, respectively, into the lower partsof the several positive compartments, Fig. 3, from which the liquid issues charged with cuprous-chlorid powder through small pipes k, that ITO branch off an exit-pipe t. The latter conveys the liquid into any suitable decanting apparatus, in which the chlorid of copper is deposited in the form of powder and the clear liquidis returned into the electrolyzer.

The clear liquid enters through a pipe j at the bottom of the vessel (1, Fig. 4, wherein after circulating-freely between the frames 0 it passes out t ough orificesk and is discharged through an exit-pipe Z. This construction of apparatus is given here merely l by way of example, and it is to be understood that the improved process may be carried into effect bymeans of any other apparatus.

Having now described my invention, what I claim as new, and desire to secure by Letters Patent, is y 1. A process for the manufacture of sulfate 5 of copper and caustic alkali, consisting in submitting anodes of copper and cathodes composed of material that is unaffected by the alkali formed to an electrolyte composed of a solution of alkaline chlorid at the negative pole and of a solution of an alkaline chlorid with cupric chlorid at the ositive pole and in collecting the 'pulverufdnt cuprous chlorid formed by the action. of the chlorin evolved at the positive pole on the copper of the anodesand converting it into sulfate of copper.

2. A process for the manufacture of sulfate of copper and caustic alkali with the produc tion of hydrochloric acid which consists in submitting anodes of copper and cathodes composed of material that is unaffected by the alkali formed to an electrolyte composed of a solution of an alkaline chlorid at the loy . positive ne ative pole and of a solution of an alkaline I .chforid with cupric chlorid at the positive pole, for obtaining caustic alkali at the negative pole and pulverulent cuprous chlorid at the positive pole collecting said cuprous chlorid, washing it in water and treating it with concentrated sulfuric acid and collecting the hydrochloric acid evolved.

3. A process for the manufacture of sulfate of copper and caustic alkali, consisting in submitting anodes of copper and cathodes composed of material that is unaffected by soda to an electrolyte composed of a solution of chlorid of sodium at the negative pole and of a saturated solution of chlorid of sodium with cupric chlorid at the positive pole and in collectin the pulverulent cuprous chlorid formed at t e positive pole and converting it into sulfate of copper.

4. A process for the manufacture of sulfate of copper and caustic alkali, consisting in submitting anodes composed of a copper aland cathodes of a material that is unaffected by the alkali formed to an electrolyte composed of a solution of an alkaline chlorid at the negative pole and of a saturated solution of an alkaline chlorid with cupric chlorid at the positive pole and in collecting the pulverulent cuprous chlorid precipitated at the pole by the action of the chlorin evolved on the copper of the anodes and con- 1 verting it into sulfate of copper.

In witness whereof I have hereunto set my hand in presence of witnesses.

HENRI MICHEL GRANIER. Witnesses:

E. DAUTREVAUX, R. ONKI, ALEXANDE LAMBERT, HANSON G; Conn. 

